US20210087347A1 - Thermoplastic elastomer composition, foamed material and manufacturing method thereof - Google Patents

Thermoplastic elastomer composition, foamed material and manufacturing method thereof Download PDF

Info

Publication number
US20210087347A1
US20210087347A1 US17/025,875 US202017025875A US2021087347A1 US 20210087347 A1 US20210087347 A1 US 20210087347A1 US 202017025875 A US202017025875 A US 202017025875A US 2021087347 A1 US2021087347 A1 US 2021087347A1
Authority
US
United States
Prior art keywords
ethylene
copolymer
thermoplastic elastomer
elastomer composition
block copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
US17/025,875
Other languages
English (en)
Inventor
Wen Wei Cheng
Hsi-Hsin Shih
Chia-Hung Hsu
Yu Tsan Tseng
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiwan Synthetic Rubber Corp
Original Assignee
Taiwan Synthetic Rubber Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiwan Synthetic Rubber Corp filed Critical Taiwan Synthetic Rubber Corp
Priority to US17/025,875 priority Critical patent/US20210087347A1/en
Publication of US20210087347A1 publication Critical patent/US20210087347A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
    • B29C44/42—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length using pressure difference, e.g. by injection or by vacuum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2331/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2431/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2431/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2431/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the present invention relates to a thermoplastic elastomer composition, particularly to a composition containing an ethylene-based copolymer, for manufacturing a foamed material.
  • Supercritical fluid foaming is one of the technologies that have achieved lightweight materials in recent years and is more environmentally friendly. At a specific temperature and pressure, gases such as nitrogen or carbon dioxide are dissolved in the polymer in a supercritical state, and then the pressure is released to nucleate the bubbles, thereby making the material lighter.
  • gases such as nitrogen or carbon dioxide
  • the use of supercritical fluid for foaming also has the problem of reduced foamed material performance after foaming. Therefore, improving the foamed material performance still continuously keeps as topics in research.
  • high-performance elastomer materials such as TPEE, TPU, and TPAE, have gradually been used for supercritical fluid foaming. However, such materials are expensive and have poor market competitiveness, and a mixture with other materials for cost down cannot reach the best performance of foamed materials.
  • low-priced ethylene-based copolymers are used to make foamed materials, such as those described in U.S. Pat. No. 9,879,133B2, TWI647262, U.S. Ser. No. 10/626,259B2, U.S. Pat. No. 9,260,578B2, TWI665242, and U.S. Pat. No. 9,493,623B2.
  • these foamed materials still have various disadvantages.
  • the present invention provides a thermoplastic elastomer composition, which can be manufactured into a foamed material.
  • a specific gravity of the foamed material is less than or equal to 0.2, preferably less than or equal to 0.16. In a preferred embodiment, a specific gravity of the foamed material is less than or equal to 0.16, a vertical rebound of the foamed material is equal to or more than 70%, and a compression set of the foamed material is less than or equal to 35%.
  • the present invention provides a thermoplastic elastomer composition for foaming.
  • the thermoplastic elastomer composition comprises: (A) an ethylene-based copolymer; (B) an olefin block copolymer; (C) an unsaturated aliphatic rubber; and (D) a crosslinking agent.
  • the olefin block copolymer is different from the ethylene-based copolymer.
  • the weight ratio of the unsaturated aliphatic rubber (C) to the olefin block copolymer (B) is 1:1.5 to 1:5.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the composition comprises 20-45 wt % of the ethylene-based copolymer (A), 30-50 wt % of the olefin block copolymer (B) and 10-25 wt % of the unsaturated aliphatic rubber (C), based on a total weight of the thermoplastic elastomer composition.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the composition comprises 30-45 wt % of the ethylene-based copolymer (A), 35-50 wt % of the olefin block copolymer (B) and 10-20 wt % of the unsaturated aliphatic rubber (C), based on the total weight of the thermoplastic elastomer composition.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the composition comprises 30-40 wt % of the ethylene-based copolymer (A) and 40-50 wt % of the olefin block copolymer (B) and 10-20 wt % of the unsaturated aliphatic rubber (C), based on the total weight of the thermoplastic elastomer composition.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the composition comprises 15-20 wt % of the unsaturated aliphatic rubber (C), based on the total weight of the thermoplastic elastomer composition.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the composition does not contain any acrylic metal salt.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the ethylene-based copolymer (A) is selected from an ethylene-based copolymer with a carbonyl group, an ethylene- ⁇ -olefin random copolymer and a combination thereof.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the ethylene-based copolymer with a carbonyl group is ethylene/vinyl acetate copolymer, ethylene/methyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/acrylic acid copolymer, ethylene/acrylic acid ionomer or a mixture thereof.
  • the ethylene-based copolymer with a carbonyl group is ethylene/vinyl acetate copolymer, ethylene/methyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/acrylic acid copolymer, ethylene/acrylic acid ionomer or a mixture thereof.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the ethylene- ⁇ -olefin random copolymer is ethylene-propylene random copolymer, ethylene-1-butene random copolymer, ethylene-1-hexene random copolymer, ethylene-1-heptene random copolymer, ethylene-1-octene random copolymer, ethylene-4-methyl-1-pentene random copolymer, ethylene-1-nonene random copolymer, ethylene-1-decene random copolymer, chlorinated polyethylene propylene-butylene random copolymer, a modified derivatives thereof, or a mixture thereof.
  • the ethylene- ⁇ -olefin random copolymer is ethylene-propylene random copolymer, ethylene-1-butene random copolymer, ethylene-1-hexene random copolymer, ethylene-1-heptene random copolymer, ethylene-1-oc
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the olefin block copolymer (B) is ethylene- ⁇ -olefin block copolymer.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the unsaturated aliphatic rubber (C) is ethylene-propylene-diene monomer rubber, butadiene rubber, butyl rubber, isoprene rubber or a mixture thereof.
  • the unsaturated aliphatic rubber (C) is ethylene-propylene-diene monomer rubber, butadiene rubber, butyl rubber, isoprene rubber or a mixture thereof.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the ethylene-based copolymer (A) is ethylene/vinyl acetate copolymer, ethylene- ⁇ -olefin random copolymer or a mixture thereof; the olefin block copolymer (B) is ethylene- ⁇ -olefin block copolymer; and the unsaturated aliphatic rubber (C) is ethylene-propylene-diene monomer rubber.
  • the ethylene-based copolymer (A) is ethylene/vinyl acetate copolymer, ethylene- ⁇ -olefin random copolymer or a mixture thereof
  • the olefin block copolymer (B) is ethylene- ⁇ -olefin block copolymer
  • the unsaturated aliphatic rubber (C) is ethylene-propylene-diene monomer rubber.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein a density range of the ethylene/vinyl acetate copolymer is 0.935-0.955 g/cm 3 ; a vinyl acetate (VA) content range of the ethylene/vinyl acetate copolymer is 14-35 wt %; the ethylene- ⁇ -olefin random copolymer is an ethylene-1-butene random copolymer, an ethylene-1-hexene random copolymer or an ethylene-1-octene random copolymer, a density range of the ethylene- ⁇ -olefin random copolymer is 0.870-0.910 g/cm 3 , and a hardness range of the ethylene- ⁇ -olefin random copolymer is 70-95 A.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the ethylene- ⁇ -olefin block copolymer is an ethylene-1-octene block copolymer, a density range of the ethylene-1-octene block copolymer is 0.860-0.890 g/cm 3 , and a hardness range of the ethylene-1-octene block copolymer is 60-85 A.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein a density range of the ethylene-propylene-diene monomer rubber is 0.870-0.910 g/cm 3 , an ethylene content range of the ethylene-propylene-diene monomer rubber is 60-85% by mass, and a weight average molecular weight range of the ethylene-propylene-diene monomer rubber is 100,000 to 200,000.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the crosslinking agent (D) is selected from the group consisting of dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne), di(tert-butylperoxyisopropyl)benzene, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane), butyl 4,4-bis(tert-butyldioxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxy isopropyl carbonate,
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the thermoplastic elastomer composition comprises 0.1-1 parts by weight of the crosslinking agent (D), based on 100 parts by weight of a total weight of the ethylene-based copolymer (A), the olefin block copolymer (B) and the unsaturated aliphatic rubber (C).
  • the crosslinking agent (D) based on 100 parts by weight of a total weight of the ethylene-based copolymer (A), the olefin block copolymer (B) and the unsaturated aliphatic rubber (C).
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the thermoplastic elastomer composition further comprises a vinyl aromatic based copolymer.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the vinyl aromatic based copolymer is a partially hydrogenated copolymer, a fully hydrogenated copolymer or a combination thereof.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the vinyl aromatic based copolymer is Styrene-Ethylene-Butylene-Styrene (SEBS) block copolymer, Styrene-Ethylene-Propylene-Styrene (SEPS) block copolymer, Styrene-Ethylene-Ethylene-Propylene-Styrene (SEEPS) block copolymer, Styrene-Ethylene-Butylene (SEB) block copolymer, Styrene-Ethylene-Propylene (SEP) block copolymer or a combination thereof.
  • SEBS Styrene-Ethylene-Butylene-Styrene
  • SEPS Styrene-Ethylene-Propylene-Styrene
  • SEEPS Styrene-Ethylene-Propylene-Styrene
  • SEB Styrene
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the vinyl aromatic based copolymer is Styrene-Butadiene-Styrene (SBS) block copolymer, Styrene-Isoprene-Styrene (SIS) block copolymer, Styrene-(Isoprene/Butadiene)-Styrene (S-(I/B)-S) block copolymer, Solution Styrene-Butadiene Rubber (SSBR), Styrene-Butadiene (SB) block copolymer, Styrene-Isoprene (SI) block copolymer or a combination thereof.
  • SBS Styrene-Butadiene-Styrene
  • SIS Styrene-Isoprene-Styrene
  • S-(I/B)-S Solution Styrene-Butadiene Rubber
  • SB Styrene-Butad
  • the present invention provides the thermoplastic elastomer composition as described above, wherein a highest peak molecular weight of the vinyl aromatic based copolymer is 80,000 to 500,000 grams per mole, more preferably 90,000 to 450,000 grams per mole, and most preferably 90,000 to 350,000 grams per mole.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein a vinyl aromatic monomer content of the vinyl aromatic based copolymer ranges from 15 to 35 wt %.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the thermoplastic elastomer composition further comprises a plasticizer, and a weight ratio of the vinyl aromatic based copolymer to the plasticizer is 2:1 to 1:2.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the plasticizer is selected from paraffin oil, naphthenic oil, aromatic oil and a composition thereof.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the thermoplastic elastomer composition comprises 20-35 wt % of the ethylene-based copolymer (A), 30-45 wt % of the olefin block copolymer (B), 10-20 wt % of the unsaturated aliphatic rubber (C), and 3-25 wt % of the vinyl aromatic based copolymer, based on the total weight of the thermoplastic elastomer composition.
  • the thermoplastic elastomer composition comprises 20-35 wt % of the ethylene-based copolymer (A), 30-45 wt % of the olefin block copolymer (B), 10-20 wt % of the unsaturated aliphatic rubber (C), and 3-25 wt % of the vinyl aromatic based copolymer, based on the total weight of the thermoplastic elastomer composition.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the thermoplastic elastomer composition comprises 35-45 wt % of the olefin block copolymer (B), 15-20 wt % of the unsaturated aliphatic rubber (C), and 5-20 wt % of the vinyl aromatic based copolymer, based on the total weight of the thermoplastic elastomer composition.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the thermoplastic elastomer composition comprises 5-10 wt % of the vinyl aromatic based copolymer, based on the total weight of the thermoplastic elastomer composition.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the thermoplastic elastomer composition is used for supercritical fluid foaming.
  • the present invention provides the thermoplastic elastomer composition as described above, wherein the thermoplastic elastomer composition further comprises a chemical foaming agent.
  • the present invention provides a compounded product, which is manufactured by mixing and melting any one of the thermoplastic elastomer compositions as described above.
  • the present invention provides a foamed material, which is prepared from any one of the thermoplastic elastomer composition as described above.
  • the present invention provides the foamed material as described above, wherein a specific gravity of the foamed material is less than or equal to 0.2, a vertical rebound of the foamed material is equal to or more than 70%, and a compression set of the foamed material is less than or equal to 35%.
  • the present invention provides the foamed material as described above, wherein the specific gravity of the foamed material is less than or equal to 0.16, and the vertical rebound of the foamed material is equal to or more than 70%, and a compression set of the foamed material is less than or equal to 35%.
  • the present invention provides the foamed material as described above, wherein the specific gravity of the foamed material is less than or equal to 0.13, and the vertical rebound of the foamed material is equal to or more than 70%, and a compression set of the foamed material is less than or equal to 35%.
  • the present invention provides the foamed material as described above, wherein the foamed material is used in construction material, transportation cushioning parts, sporting goods or shoe midsoles.
  • the present invention provides a method of making a foamed material, comprising the following steps: step 1: mixing and melting any one of the thermoplastic elastomer composition as described above to form compounded granules; step 2: melting and cross-linking the compounded granules to form a cross-linked molded body; and step 3: foaming the cross-linked molded body by a supercritical fluid to form the foamed material.
  • the present invention provides the method as described above, wherein the supercritical fluid is nitrogen, carbon dioxide or a mixture thereof.
  • the present invention provides a method of making a foamed material, comprising the following steps: step 1: mixing and melting any one of the thermoplastic elastomer composition as described above to form compounded granules, wherein the thermoplastic elastomer composition further comprises a chemical foaming agent; and step 2: melting and cross-linking the compounded granules, during which the compounded granules are foamed to form the foamed material.
  • Density/specific gravity measured according to ASTM D792 standard.
  • Compression set measured according to ASTM D395 standard.
  • Highest peak molecular weight of the vinyl aromatic based copolymer measured by gel permeation chromatography, which is a measurement method well known to those skilled in the art.
  • Vinyl aromatic monomer content of the vinyl aromatic based copolymer measured by nuclear magnetic resonance analyzer, which is a measurement method well known to those skilled in the art.
  • thermoplastic elastomer composition for foaming of the present invention comprises: (A) an ethylene-based copolymer; (B) an olefin block copolymer, which is different from the ethylene-based copolymer; (C) an unsaturated aliphatic rubber; and (D) a crosslinking agent, in which the weight ratio of the unsaturated aliphatic rubber (C) to the olefin block copolymer (B) is 1:1.5 to 1:5.
  • the thermoplastic elastomer composition of the present invention does not contain any acrylic metal salt.
  • the acrylic metal salt is prone to agglomerate under high pressure or moisture, and further affects the uniformity of kneading.
  • the temperature is higher than 90° C.
  • the acrylic metal salt will undergo self-polymerization reaction, which will reduce its reactivity with polymers during crosslinking. Therefore, the thermoplastic elastomer composition excluding the use of acrylic metal salt has the characteristics of easy processing.
  • the composition comprises 20-45 wt % of the ethylene-based copolymer (A), 30-50 wt % of the olefin block copolymer (B) and 10-25 wt % of the unsaturated aliphatic rubber (C), based on the total weight of the composition.
  • the composition comprises 30-45 wt % of the ethylene-based copolymer (A), 35-50 wt % of the olefin block copolymer (B) and 10-20 wt % of the unsaturated aliphatic rubber (C).
  • the composition comprises 30-40 wt % of the ethylene-based copolymer (A) and 40-50 wt % of the olefin block copolymer (B). In another more preferred embodiment, the composition comprises 15-20 wt % of the unsaturated aliphatic rubber (C).
  • the ethylene-based copolymer (A) is any copolymer containing ethylene as a monomer, in which the content of the ethylene monomer exceeds 50 wt %.
  • the ethylene-based copolymer (A) is selected from the ethylene-based copolymers with a carbonyl group and the ethylene- ⁇ -olefin random copolymers.
  • the ethylene-based copolymer with a carbonyl group is ethylene/vinyl acetate copolymer, ethylene/methyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/acrylic acid copolymer, ethylene/acrylic add ionomer or a mixture thereof; and the ethylene- ⁇ -olefin random copolymer is ethylene-propylene random copolymer, ethylene-1-butene random copolymer, ethylene-1-hexene random copolymer, ethylene-1-heptene random copolymer, ethylene-1-octene random copolymer, ethylene-4-methyl-1-pentene random copolymer, ethylene-1-nonene random copolymer, ethylene-1-decene random copolymer, chlorinated polyethylene propylene
  • the olefin block copolymer (B) comprises a rigid segment composed of repeating units of, for example, ethylene or propylene and a flexible segment composed of repeating units of, for example, ⁇ -olefin.
  • the olefin block copolymer (B) is different from the ethylene-based copolymer (A).
  • the olefin block copolymer (B) is an ethylene- ⁇ -olefin block copolymer.
  • the ⁇ -olefin may be 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene, among which 1-octene is preferred.
  • the repeating unit of the ⁇ -olefin may be a repeating unit obtained from at least one of the aforementioned ⁇ -olefins.
  • the unsaturated aliphatic rubber (C) is a polymer of olefin monomers and/or diene monomers, where unsaturation means that the polymer structure contains at least one double bond.
  • the unsaturated aliphatic rubber (C) is different from the ethylene-based copolymer (A) and the olefin block copolymer (B).
  • the unsaturated aliphatic rubber (C) is an ethylene-propylene-diene monomer rubber, butadiene rubber, butyl rubber, isoprene rubber, or a mixture thereof.
  • the unsaturated aliphatic rubber (C) is a ternary copolymer composed of ethylene monomers, propylene monomers, and a small amount of diene monomers, wherein the diene monomers may have double bonds remaining after polymerization for vulcanization of the rubbers.
  • the diene monomer may be ethylidene norbornene (ENB), vinyl norbornene (VNB), dicyclopentadiene (DCPD), and the content thereof may be 0.5 to 10 wt %.
  • the ethylene-based copolymer (A) of the thermoplastic elastomer composition is ethylene/vinyl acetate copolymer or an ethylene- ⁇ -olefin random copolymer;
  • the olefin block copolymer (B) of the thermoplastic elastomer composition is ethylene- ⁇ -olefin block copolymer;
  • the unsaturated aliphatic rubber (C) of the thermoplastic elastomer composition is an ethylene-propylene-diene monomer rubber.
  • the ethylene/vinyl acetate copolymer has a density range of 0.935-0.955 g/cm 3 and a vinyl acetate (VA) content range of 14-35 wt %.
  • the ethylene- ⁇ -olefin random copolymer is an ethylene-1-butene random copolymer, an ethylene-1-hexene random copolymer or an ethylene-1-octene random copolymer with a density range of 0.870-0.910 g/cm 3 and a hardness range of 70-95 A.
  • the ethylene- ⁇ -olefin block copolymer is an ethylene-1-octene block copolymer with a density in the range of 0.860-0.890 g/cm 3 and a hardness in the range of 60-85 A.
  • the ethylene-propylene-diene monomer rubber has a density range of 0.870-0.910 g/cm 3 , an ethylene content range of 60-85% by mass, and a weight average molecular weight range of 100,000 to 200,000.
  • the crosslinking agent (D) is an additive with the cross-linking effect, and is generally an organic peroxide.
  • the crosslinking agent (D) is preferably selected from the group consisting of dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne), di(tert-butylperoxyisopropyl)benzene, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane), butyl 4,4-bis(tert-butyldioxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl
  • the crosslinking agent (D) is 0.1-1 parts by weight, based on 100 parts by weight of the total weight of the ethylene-based copolymer (A), the olefin block copolymer (B) and the unsaturated aliphatic rubber (C).
  • a crosslinking aid may be additionally added, such as triallyl cyanurate (TAC) or triallyl isocyanurate (TAIC).
  • TAC triallyl cyanurate
  • TAIC triallyl isocyanurate
  • the crosslinking aid helps to co-vulcanize with the thermoplastic elastomer, which can improve the crosslinking speed and crosslink density of the thermoplastic elastomer, thereby improving the heat resistance and weather resistance of the elastomer material.
  • the thermoplastic elastomer composition of the present invention may further optionally include a vinyl aromatic based copolymer.
  • the content of the vinyl aromatic based copolymer is 3-25 wt %, 5-20 wt %, or 5-10 wt %. More preferably, the highest peak molecular weight of the vinyl aromatic based copolymer is 80,000 to 500,000 grams per mole, more preferably 90,000 to 450,000 grams per mole, and most preferably 90,000 to 350,000 grams per mole.
  • the vinyl aromatic monomer content of the vinyl aromatic based copolymer is 15 to 35 wt %.
  • a plasticizer may be optionally added. In a preferred embodiment, the weight ratio of the vinyl aromatic based copolymer to the plasticizer is 2:1 to 1:2.
  • the composition comprises 20-35 wt % of the ethylene-based copolymer (A), 30-45 wt % of the olefin block copolymer (B), 10-20 wt % of the unsaturated aliphatic rubber (C), and 3-25 wt % of the vinyl aromatic based copolymer.
  • the composition comprises 35-45 wt % of the olefin block copolymer (B), 15-20 wt % of the unsaturated aliphatic rubber (C), and 5-20 wt % of the vinyl aromatic based copolymer.
  • the composition comprises 5-10 wt % of the vinyl aromatic based copolymer.
  • the monomers of the vinyl aromatic based copolymer are vinyl aromatic monomers and conjugated diene monomers.
  • the conjugated diene monomer suitable for the present invention can be a conjugated diene containing 4 to 12 carbon atoms, and specific examples thereof include: 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 2-p-tolyl-1,3-butadiene, 2-benzyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 3-methyl-1,3-hexadiene, 3-butyl-1,3-octadiene, 3-phenyl-1,3-pentadiene, 4-
  • vinyl aromatic monomers suitable for the present invention include: styrene, methylstyrene and all isomers thereof, ethylstyrene and all isomers thereof, tert-butyl styrene and all isomers thereof, dimethylstyrene and all isomers thereof, methoxystyrene and all isomers thereof, cyclohexylstyrene and all isomers thereof, vinylbiphenyl, 1-vinyl-5-hexylnaphthalene, vinylnaphthalene, vinylanthracene, 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, divinylnaphthalene, tert-butoxystyrene, 4-propyl styrene, 4-dodecylstyrene, 2-ethyl
  • the vinyl aromatic based copolymer may be a block, random or taper arranged polymer of two monomers mentioned above or other suitable polymeric monomers, among which the block copolymer is preferred, and the triblock copolymer is more preferred.
  • the vinyl aromatic based copolymer may be selected from non-hydrogenated copolymers, hydrogenated copolymers or a combination thereof.
  • the hydrogenated copolymer may be a partially hydrogenated copolymer (the unsaturated double bond of the conjugated diene monomer having a hydrogenation rate of 10-90%) or a fully hydrogenated copolymer (the unsaturated double bond of the conjugated diene monomer having a hydrogenation rate of >90%).
  • the vinyl aromatic based copolymer is the hydrogenated copolymer.
  • the vinyl aromatic based copolymer also includes the linear copolymer, the radial copolymer, the branched copolymer, or the asymmetry copolymer.
  • the vinyl aromatic based copolymer is the linear copolymer.
  • Preferred examples of the hydrogenated vinyl aromatic based copolymer are Styrene-Ethylene-Butylene-Styrene (SEBS) block copolymers, Styrene-Ethylene-Propylene-Styrene (SEPS) block copolymers, Styrene-Ethylene-Ethylene-Propylene-Styrene (SEEPS) block copolymers, Styrene-Ethylene-Butylene (SEB) block copolymers, Styrene-Ethylene-Propylene (SEP) block copolymers or various combinations thereof.
  • SEBS Styrene-Ethylene-Butylene-Styrene
  • SEPS Styrene-Ethylene-Propylene-Styrene
  • SEEPS Styrene-Ethylene-Propylene-Styrene
  • SEB Styrene-Ethylene-Propylene
  • non-hydrogenated vinyl aromatic based copolymers are Styrene-Butadiene-Styrene (SBS) block copolymers, Styrene-Isoprene-Styrene (SIS) block copolymers, Styrene-(Isoprene/Butadiene)-Styrene (S-(I/B)-S) block copolymers, Solution Styrene-Butadiene Rubber (SSBR), Styrene-Butadiene (SB) block copolymers, Styrene-Isoprene (SI) block copolymers or various combinations thereof.
  • SBS Styrene-Butadiene-Styrene
  • SIS Styrene-Isoprene-Styrene
  • S-(I/B)-S Solution Styrene-Butadiene Rubber
  • SB Styrene-Butadiene
  • SI Styrene-Isoprene
  • the plasticizer is selected from paraffin oil, naphthenic oil, aromatic oil and a composition thereof.
  • the present invention may also add other processing aid, which is selected from a tackifier, a plasticizer and a melt strength enhancer.
  • the tackifier may be a rosin resin, a petroleum-based resin, a terpene resin or an oligomer.
  • the oligomer is polymerized from a plurality of identical or different structural units. The weight average molecular weight of the oligomer is less than 10,000.
  • the oligomer is polymerized from monomers of ethylene, butene, styrene or combinations of the above.
  • the plasticizer is an additive that increases the softness of the material or liquefies the material.
  • the plasticizer is the fatty oil-based plasticizer or the epoxidized oil-based plasticizer.
  • the fatty oil-based plasticizer is glycerin, castor oil, soybean oil, or zinc stearate.
  • the epoxidized oil-based plasticizer is epoxidized soybean oil or epoxidized linseed oil.
  • the melt strength enhancer is an additive that increases the melt strength of materials.
  • the melt strength enhancer is the fluoride-containing compound, among which polytetrafluoroethylene (PTFE) is preferred.
  • thermoplastic elastomer composition of the present invention may optionally comprise a chemical foaming agent.
  • a known and suitable organic foaming agent or inorganic foaming agent may be used.
  • the organic foaming agent may include an azo compound, a nitroso compound, a sulfonyl hydrazide compound, and the like.
  • azo compound examples include azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), diisopropyl azodiformate (DIPA), barium azodicarboxylate (BaAC), diethyl azodicarboxylate (Azoform E), diazoamino benzene, barium azodicarboxylate, etc.
  • nitroso compound examples include N,N′-dinitrosopentamethylenetetramine (DPT), N,N′-dinitroso-N,N′-dimethyl terephthalamide (NTA), etc.
  • the sulfonyl hydrazine compound examples include benzenesulfonyl hydrazine, p-toluenesulfonyl hydrazide (TSH), 4,4′-oxybis(benzenesulfonyl hydrazide) (OBSH), diphenylsulfone-3,3′-disulfonyl hydrazide, benzene-1,3-disulphohydrazide, p-toluenesulfonyl semicarbazide, 4,4′-oxybis(benzenesulfonyl semicarbazide), trihydrazinotriazine (THT), 5-phenyltetrazole, etc.
  • the inorganic foaming agent may include sodium bicarbonate, potassium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, sodium borohydride, and metal powders, etc.
  • the method for manufacturing a foamed material according to the present invention may be performed by chemical foaming or physical foaming.
  • the chemical foaming may use the thermoplastic elastomer composition containing the chemical foaming agent.
  • the physical foaming is preferred to use thermoplastic elastomer composition containing no chemical foaming agent.
  • the method for manufacturing a foamed material by physical foaming includes the following steps: step 1: mixing and melting the thermoplastic elastomer composition as described above to form compounded granules, wherein the thermoplastic elastomer composition does not contain the chemical foaming agent; step 2: melting and cross-linking the compounded granules to form a cross-linked molded body; and step 3: foaming the cross-linked molded body by physical foaming to form the foamed material.
  • the compounded granules are pellets obtained by kneading and extruding the thermoplastic elastomer composition.
  • the shape of the compounded granules is not particularly limited, and may be a round shape, a sheet/film shape, a strand like, or crumb like.
  • the step 2 of the physical foaming further comprises pressing a plurality of the compounded granules into a sheet through calendering process to remove bubbles, and then placing the sheet in a mold for hot pressing, melting and crosslinking to form the cross-linked molded body.
  • the step 2 of the physical foaming includes performing hot-pressing and cross-linking by melt-injecting the compounded granules into a mold using an injection machine to form the cross-linked molded body.
  • the step 3 of the physical foaming is to impregnate the cross-linked molded body in a supercritical fluid for a period of time and then release the pressure so as to form the foamed material.
  • the supercritical fluid may be carbon dioxide, nitrogen or a mixture thereof.
  • the method for manufacturing a foamed material by chemical foaming includes the following steps: step 1: mixing and melting the thermoplastic elastomer composition as described above to form compounded granules, wherein the thermoplastic elastomer composition contains the chemical foaming agent; step 2: placing the compounded granules in a heated mold for melting and crosslinking, during which the compounded granules are foamed to form the foamed material.
  • the shape of the compounded granules is not particularly limited, and may be a round shape, a sheet/film shape, a strand like, or crumb like.
  • the step 2 of the chemical foaming further comprises pressing a plurality of the compounded granules into a sheet through calendering process to remove bubbles, and then placing the sheet in the heated mold for hot pressing, melting and crosslinking for molding, during which the chemical foaming agent produces foaming effect to form the foamed material.
  • the step 2 of the chemical foaming includes melt-injecting the compounded granules into a mold by an injection machine to perform hot-pressing and cross-linking for molding, during which the chemical foaming agent produces foaming effect to form the foamed material.
  • thermoplastic elastomer composition used in some examples or comparative examples of the present invention are as follows.
  • Olefin block copolymer (B) Dow Infuse 9530 (marked as OBC-1(B-1) in the table), Dow Infuse 9107 (marked as OBC-2(B-2) in the table), Dow Infuse 9100 (marked as OBC-3(B-3) in the table).
  • Crosslinking aid (E) Kettlitz TAC/GR 50 (marked as TAC-50(E) in the table)
  • Vinyl aromatic based copolymer TSRC Taipol 6151 (32 wt % of styrene content, 330,000 g/mol of Mp, being marked as SEBS-1 in the tables), TSRC Taipol 6014 (18 wt % of styrene content, 95; 000 g/mol of Mp, being marked as SEBS-2 in the tables).
  • Plasticizer Idemitsu E-oil (marked as Oil in the table)
  • Example 1 Physical foaming was carried out in Example 1.
  • the ingredients of the composition of Example 1 as shown in Table 1 were dry mixed and put into a 5-liter kneader.
  • the temperature of the machine was set at 100-120° C., and the rotation speed was 40-80 RPM.
  • the mixture was put into a granulator for forming the compounded granules.
  • the multiple compounded granules were melted and calendered into a sheet by a double-roller kneader, and the temperature of the roller was 100-120° C. Afterwards, the sheet was placed in the mold to perform cross-linking and molding by hot pressing.
  • the mold temperature was set at 175 ⁇ 2° C., and the time was 390-450 seconds to obtain the cross-linked molded body.
  • the cross-linked molded body was naturally cooled to room temperature to avoid residual stress.
  • the cross-linked molded body was put into the supercritical fluid autoclave, and then the supercritical nitrogen was injected into the autoclave.
  • the saturation temperature was 100-170° C.
  • the saturation pressure was 10-30 Mpa
  • the saturation time was 0.5-5 hours.
  • a foamed material was obtained after pressure relief. After the foamed material was left for 24 hours, various physical property tests were conducted.
  • Table 2 shows examples of the composition having not more than 25 wt % of the vinyl aromatic based copolymer with respect to the total weight of the composition. From Table 1 and Table 2, it can be seen that when the weight ratio of the unsaturated aliphatic rubber (C) to the olefin block copolymer (B) is 1:1.5 to 1:5, by adding the vinyl aromatic based copolymer, the foamed material which is lighter and has a lower specific gravity (0.11 ⁇ 0.13 g/cm 3 ) and remains in a good vertical rebound (not less than 70%), can be obtained. Referring to Table 2, the addition ratio of the vinyl aromatic based copolymers of Examples 7 to 11 is not more than 20 wt % of the total weight of the composition.
  • the foamed materials prepared from Examples 7 to 11 have better compression set.
  • the addition ratio of the vinyl aromatic based copolymers of Examples 8 to 11 is 5 to 10 wt % of the total weight of the composition.
  • the foamed materials prepared from Examples 8 to 11 have better compression set.
  • Example-4 Example-5 11
  • Example-6 Example-7
  • EPDM(C) 20 0 30.8 18 0 18 SEBS-1 0 0 0 0 0 SEBS-2 0 0 0 10 12.2 10 Oil 0 0 0 0 0 0 EVA(A-2) 45 56.25 69.2 27.5 33.5 27.5 OBC-1(B-1) 0 0 0 24.2 29.5 0 OBC-2(B-2) 35 43.75 0 20.3 24.8 0 POE(A-3) 0 0 0 0 0 24.2 POE(A-4) 0 0 0 0 0 20.3 BIBP(D, phr*) 0.25 0.25 0.25 0.25 0.25 0.25 0.25 TAC-50(E, phr*) 0.75 0.75 0.75 0.75 0.9 0.9 0.9
  • Physical properties 0.14 0.14 0.16 0.13 0.14 0.19 (g/cm
  • Table 3 shows that the composition containing the unsaturated aliphatic rubber (C) and the olefin block copolymer (B) may have better characteristics.
  • the composition of Comparative Example 4 does not contain the unsaturated aliphatic rubber (C)
  • the composition of Comparative Example 5 does not contain the olefin block copolymer (B).
  • Example 3 has better vertical rebound and compression set.
  • Example 3 in Table 3 is a composition that does not contain the vinyl aromatic based copolymer.
  • Example 11 in Table 3 is a composition containing the vinyl aromatic based copolymer. Compared with Comparative Example 6 (without the unsaturated aliphatic rubber (C)) and Comparative Example 7 (without the olefin block copolymer (B)), Example 11 has better vertical rebound and compression set.
  • Physical foaming is a preferred embodiment of the present invention.
  • the multiple compounded granules were melted and calendered into a sheet by a double-roller kneader, and the temperature of the roller was 100-120° C. Afterwards, the sheet was placed in the mold to perform cross-linking and molding by hot pressing. The mold temperature was set at 175 ⁇ 2° C., and the time was 390-450 seconds. During the melting and crosslinking process, the chemical foaming agent produced foaming effect to form the foamed materials.
  • the present invention further comprises manufacturing the articles which can be used in construction material, transportation cushioning parts, sporting goods or shoe midsoles from the foamed material as described above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)
US17/025,875 2019-09-19 2020-09-18 Thermoplastic elastomer composition, foamed material and manufacturing method thereof Pending US20210087347A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/025,875 US20210087347A1 (en) 2019-09-19 2020-09-18 Thermoplastic elastomer composition, foamed material and manufacturing method thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201962902573P 2019-09-19 2019-09-19
US17/025,875 US20210087347A1 (en) 2019-09-19 2020-09-18 Thermoplastic elastomer composition, foamed material and manufacturing method thereof

Publications (1)

Publication Number Publication Date
US20210087347A1 true US20210087347A1 (en) 2021-03-25

Family

ID=72603294

Family Applications (1)

Application Number Title Priority Date Filing Date
US17/025,875 Pending US20210087347A1 (en) 2019-09-19 2020-09-18 Thermoplastic elastomer composition, foamed material and manufacturing method thereof

Country Status (5)

Country Link
US (1) US20210087347A1 (fr)
EP (1) EP3795630A3 (fr)
KR (1) KR102528735B1 (fr)
CN (1) CN112521711A (fr)
TW (1) TWI816051B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116041836A (zh) * 2022-12-30 2023-05-02 福建省莆田市联盛鞋业有限公司 一种超高回弹eva化学发泡鞋底材料及其制备工艺
CN116656035A (zh) * 2023-06-25 2023-08-29 安踏（中国）有限公司 一种射出高倍率改性聚酯tpee发泡材料

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102631510B1 (ko) * 2021-05-31 2024-01-31 한국소재융합연구원 내구성이 우수한 경량 신발 중창용 발포체 조성물

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4680317A (en) * 1981-08-17 1987-07-14 Dynamit Nobel Aktiengesellschaft Molding composition for crosslinked foam material from polyolefins and ethylene-propylene elastomer, and process for the production of the foam material
US20070129454A1 (en) * 2005-12-05 2007-06-07 Tsrc Corporation Thermoplastic elastomer foaming material and the manufacturing method thereof
US20150038606A1 (en) * 2013-08-02 2015-02-05 Nike, Inc. Low density foamed articles and methods for making
KR101574638B1 (ko) * 2014-12-29 2015-12-07 주식회사 미래텍 자동차 플로어 카페트용 올레핀 블럭 공중합체 수지조성물과 발포체 및 그 제조방법
US20160168345A1 (en) * 2014-12-12 2016-06-16 Clopay Plastic Products Company, Inc. Elastomeric compositions for blown-film extrusion
US9493623B2 (en) * 2008-12-22 2016-11-15 Asahi Kasei Chemicals Corporation Crosslinkable and foamable composition, crosslinked foam, and shoe midsole comprising the same

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9260578B2 (en) 2005-11-30 2016-02-16 Tsrc Corporation Thermoplastic elastomer foaming material
CN101959942B (zh) * 2007-12-28 2013-05-08 陶氏环球技术有限责任公司 用于制备吸振垫的具有高填充量的基于pe的交联弹性泡沫体以及用于鞋用制品和地面材料应用的制品
KR101180874B1 (ko) * 2010-06-17 2012-09-07 호남석유화학 주식회사 발포 성형성이 향상된 열가소성 가교 탄성체 조성물, 및 상기 조성물에 의해 형성된 성형품
JP6147281B2 (ja) * 2012-03-16 2017-06-14 ダウ グローバル テクノロジーズ エルエルシー 発泡性組成物、発泡体及びその物品
WO2014101154A1 (fr) * 2012-12-31 2014-07-03 Dow Global Technologies Llc Vulcanisat thermoplastique comprenant un copolymère bloc oléfinique réticulé
CN103992609A (zh) * 2014-05-20 2014-08-20 泉州三盛橡塑发泡鞋材有限公司 一种烯烃嵌段共聚物泡沫材料及其制备方法
CN104804297B (zh) * 2015-04-24 2018-08-28 茂泰(福建)鞋材有限公司 一种轻量高弹eva鞋底及其制备方法
KR101763242B1 (ko) * 2015-11-20 2017-08-01 주식회사 미래텍 자동차 플로어 카페트용 폼 패드 및 그 제조 방법
CN105585769A (zh) * 2016-03-14 2016-05-18 福建省长立网络科技有限公司 一种高耐磨弹性发泡橡胶材料及其制备方法
JP2019514451A (ja) 2016-03-15 2019-06-06 ナイキ イノヴェイト シーヴィーＮｉｋｅ Ｉｎｎｏｖａｔｅ Ｃ．Ｖ． 発泡体組成物及びその使用
CN106009463A (zh) * 2016-06-17 2016-10-12 广东锐铂耐特新材料有限公司 一种合成橡胶发泡材料及其制备方法
ES2816007T3 (es) 2017-01-25 2021-03-31 Tsrc Corp Composición termoplástica de elastómero para espuma entrecruzada y uso de la misma
CN107383567A (zh) * 2017-03-15 2017-11-24 墨烯材料科技有限公司 一种石墨烯/聚合物轻质高弹柔软复合发泡材料及其制备方法
CN106905599B (zh) * 2017-04-21 2020-03-03 安踏（中国）有限公司 一种轻质高弹eva复合发泡材料及其制备方法和应用
CN107501713B (zh) * 2017-09-30 2020-06-23 特步(中国)有限公司 一种透光发泡鞋底组合物及采用该组合物制作鞋底的方法
TWI647262B (zh) * 2018-02-14 2019-01-11 三晃股份有限公司 Polyolefin elastomer composition and foamed elastomer
CN108676242A (zh) * 2018-05-17 2018-10-19 谢冠华 一种具有透光功能的鞋底及其制备方法
CN108892853A (zh) * 2018-05-24 2018-11-27 中国人民解放军62023部队 一种抗热收缩橡塑共混发泡中底及其配方
CN108774378B (zh) * 2018-05-25 2021-04-06 厦门乔丹科技有限公司 一种高弹缓震橡塑材料、缓震高弹鞋底及其制备工艺
US10626259B2 (en) 2018-07-05 2020-04-21 Sunko Ink Co., Ltd. Polyolefin elastomer composite and foamed elastomer
CN109679264A (zh) * 2018-12-21 2019-04-26 三六一度(中国)有限公司 一种高弹鞋底材料及其制备方法及采用该材料的鞋底

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4680317A (en) * 1981-08-17 1987-07-14 Dynamit Nobel Aktiengesellschaft Molding composition for crosslinked foam material from polyolefins and ethylene-propylene elastomer, and process for the production of the foam material
US20070129454A1 (en) * 2005-12-05 2007-06-07 Tsrc Corporation Thermoplastic elastomer foaming material and the manufacturing method thereof
US9493623B2 (en) * 2008-12-22 2016-11-15 Asahi Kasei Chemicals Corporation Crosslinkable and foamable composition, crosslinked foam, and shoe midsole comprising the same
US20150038606A1 (en) * 2013-08-02 2015-02-05 Nike, Inc. Low density foamed articles and methods for making
US20160168345A1 (en) * 2014-12-12 2016-06-16 Clopay Plastic Products Company, Inc. Elastomeric compositions for blown-film extrusion
KR101574638B1 (ko) * 2014-12-29 2015-12-07 주식회사 미래텍 자동차 플로어 카페트용 올레핀 블럭 공중합체 수지조성물과 발포체 및 그 제조방법

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Dow Engae 8003 POE MatWeb (Year: 2015) *
Dow Infuse 9530 Tech. Data Sheet (Year: 2016) *
English machine translation of KR101574638 (Year: 2015) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116041836A (zh) * 2022-12-30 2023-05-02 福建省莆田市联盛鞋业有限公司 一种超高回弹eva化学发泡鞋底材料及其制备工艺
CN116656035A (zh) * 2023-06-25 2023-08-29 安踏（中国）有限公司 一种射出高倍率改性聚酯tpee发泡材料

Also Published As

Publication number Publication date
TW202112955A (zh) 2021-04-01
KR102528735B1 (ko) 2023-05-03
EP3795630A3 (fr) 2021-04-28
EP3795630A2 (fr) 2021-03-24
CN112521711A (zh) 2021-03-19
KR20210035053A (ko) 2021-03-31
TWI816051B (zh) 2023-09-21

Similar Documents

Publication Publication Date Title
KR102528735B1 (ko) 열가소성 엘라스토머 조성물, 발포 재료 및 이의 제조 방법
US9493623B2 (en) Crosslinkable and foamable composition, crosslinked foam, and shoe midsole comprising the same
KR100726276B1 (ko) 발포체용 수지 조성물 및 그 용도
JP5204482B2 (ja) 発泡体用樹脂組成物およびその用途
JP5394757B2 (ja) 架橋発泡用組成物及び架橋発泡体、並びにそれを用いた履物及び積層体
TWI665242B (zh) 交聯發泡用熱塑性彈性體組合物及其應用
US11939456B2 (en) Composition for preparing a foam, foam, and shoe employing the same
US11746226B2 (en) Polymer composition, foam and method thereof
JP2000344925A (ja) オレフィン系エラストマー架橋発泡体およびその架橋発泡体用エラストマー組成物
JP2022183099A (ja) 架橋性及び発泡性組成物、それによって得られる発泡体、発泡のための組成物並びにその使用
CN116970253A (zh) 发泡体用组合物、发泡体和发泡体的制造方法
JP2023164301A (ja) 発泡体用組成物、発泡体、及び発泡体の製造方法
JPH0273846A (ja) 熱可塑性エラストマーの製造方法

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: APPLICATION DISPATCHED FROM PREEXAM, NOT YET DOCKETED

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER